CN110655718A - Low-density, high-rigidity and high-toughness polypropylene composite material and preparation method thereof - Google Patents
Low-density, high-rigidity and high-toughness polypropylene composite material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention discloses a low-density, high-rigidity and high-toughness polypropylene composite material and a preparation method thereof, wherein the low-density, high-rigidity and high-toughness polypropylene composite material is prepared by mixing, extruding and granulating 42-61 parts of polypropylene, 8-12 parts of chopped glass fiber, 14-18 parts of toughening agent, 12-20 parts of hollow glass microsphere, 5-8 parts of compatilizer, 0.2-0.5 part of antioxidant and 0.2-0.5 part of other auxiliary agents. The invention disclosesThe low-density, high-rigidity and high-toughness polypropylene composite material adopts high-crystallinity copolymerized polypropylene as a base material, and provides a basic guarantee for obtaining high rigidity of the prepared composite material; the surface of the hollow glass microsphere is treated by the silane coupling agent, and the compatilizer with high maleic anhydride content is added, so that the bonding strength of the hollow glass microsphere, the glass fiber and the polypropylene is enhanced, and the finally prepared composite material has higher strength; the polypropylene composite material prepared by the invention has the tensile strength of more than 20MPa, the flexural modulus of more than 2000MPa and the notch impact strength of more than 20KJ/m2Has good sensitivity and toughness, and the density is only 0.88-0.92g/cm3And the requirement of light weight is met.
Description
Technical Field
The invention relates to the field of modification of high polymer materials, in particular to a low-density, high-rigidity and high-toughness polypropylene composite material and a preparation method thereof.
Background
The polypropylene has the advantages of good mechanical property, no toxicity, low relative density, heat resistance, chemical resistance, easy processing and forming and the like, and the price is low. The resin can be endowed with outstanding physical and mechanical properties through processing modification, and therefore, certain engineering plastics are replaced, great progress is made in the aspect of universal plastic engineering in recent years, and the resin is the most rapidly-growing variety and the most actively-developed new variety among five general synthetic resins.
With the rapid development of science and technology, the requirements of various large host computer factories in the automobile industry on materials are changed newly, and particularly with the implementation plan of issuing a new round of file for the comprehensive oil consumption requirements of automobiles at home and abroad in recent years, the light weight of automobiles becomes a research hotspot of various large host computer factories. Therefore, various plastic modification enterprises develop towards light weight of materials, resource saving, high performance and high function.
In the prior art, the traditional mineral filled modified polypropylene material is widely applied to interior and exterior parts of automobiles, for example, the traditional instrument board, door panel, upright post and the like are made of PP + EPDM-T20 material, and the density is 1.04-1.07g/cm3The requirement of the automobile industry for light weight of materials is increasingly not met. The traditional method for reducing the density is to reduce the content of filling minerals, so that although the density of the material can be reduced, the rigidity, the strength and the like of the material cannot meet the requirements of the materialActual performance design requirements.
Therefore, a material with lower density than the traditional PP + EPDM-T20 material and other properties such as rigidity, toughness, fluidity, shrinkage rate and the like consistent with or even higher than those of the PP + EPDM-T20 material is urgently needed.
Disclosure of Invention
The invention aims to provide a low-density, high-rigidity and high-toughness polypropylene composite material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a low-density, high-rigidity and high-toughness polypropylene composite material is characterized in that: the composition is prepared from the following components in parts by weight:
in a further scheme, the polypropylene is high-crystalline co-polypropylene.
The chopped glass fiber is alkali-free glass fiber, the diameter D is 5.0-15.0 μm, and the length is 4 mm.
The toughening agent is at least one of ethylene-octene copolymer and ethylene-propylene copolymer, the melt flow rate of the toughening agent is 0.5-20 g/10min under the condition of 190 ℃/2.16kg, and the density of the toughening agent is 0.86-0.89g/cm3。
The particle size D50 of the hollow glass bead is 5-30 mu m, and the density is 0.4-0.6g/cm3The compressive strength is more than or equal to 20MPa, and the hollow glass microspheres are surface-treated by a silane coupling agent.
The processing method comprises preparing 25% (mass ratio) ethanol solution with silane coupling agent, and adding acetic acid to adjust pH to 4.5-5.5; the hollow glass beads are placed in a mixer to be stirred at a low speed of 40-60 r/min, and a prepared silane coupling agent alcohol solution with the mass of 1-2.5% of the glass beads is added in a spraying mode to be treated for 5-15 min.
The compatilizer is one or a mixture of more of maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted polypropylene and maleic anhydride grafted polypropylene, wherein the content of maleic anhydride is 1.5-3.5%.
The antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076), tri- (2, 4-di-tert-butylphenyl) phosphite (168) and dioctadecyl thiodipropionate (DSTDP).
The other auxiliary agents comprise a coupling agent, a lubricating agent and a dispersing agent.
Another object of the present invention is to provide a method for preparing a low-density, high-rigidity, high-toughness polypropylene composite material, comprising the steps of:
(1) 42-61 parts of polypropylene, 14-18 parts of toughening agent, 5-8 parts of compatilizer, 0.2-0.5 part of antioxidant and 0.2-0.5 part of other auxiliary agent are mixed and added into a high-speed mixer to be mixed for 5-15 min;
(2) adding the uniformly mixed materials obtained in the step (1) into a double-screw extruder, adding 8-12 parts of chopped glass fiber and 12-20 parts of hollow glass beads into a side feeding port of the double-screw extruder, and melting, blending and extruding the materials together to obtain a low-density, high-rigidity and high-toughness polypropylene composite material;
wherein, the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-crystallinity copolymerized polypropylene is adopted as a base material, so that basic guarantee is provided for high rigidity of the prepared composite material;
(2) the hollow glass microspheres with the compressive strength of more than or equal to 20MPa are selected, and the crushing rate of the hollow glass microspheres is reduced in a side feeding processing mode, so that the density of the composite material is reduced fundamentally;
(3) the silane coupling agent is used for treating the surface of the glass microsphere, and the compatilizer with high maleic anhydride content is added, so that the bonding strength of the glass microsphere, the glass fiber and the polypropylene is enhanced, and the finally prepared composite material has higher strength;
(4) the polypropylene composite material prepared by the invention has tensile strengthGreater than 20MPa, flexural modulus greater than 2000MPa, and notched impact strength greater than 20KJ/m2Has good rigidity and toughness, and the density is only 0.88-0.92g/cm3And the requirement of light weight is met.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate, but not limit the invention.
The available types and manufacturer information of each component are as follows:
polypropylene: PP BX3800, PP BX3900, PP BX3920 produced by SK, PP-EA5074 produced by Basel
Chopped glass fiber 508A produced by chemical megalithic stone, 248A produced by Erwining and 305K produced by Chongqing international composite material
Hollow glass beads: IM16K manufactured by 3M
A compatilizer: PP-G1001 produced by Polyram
A toughening agent: POE8200, POE8150 and POE8137 produced by Dow chemical production
The other auxiliary agents are typical products sold in the market.
Wherein, the surface of the hollow glass bead is treated by silane coupling agent, the treatment method is that the silane coupling agent is prepared into 25% (mass ratio) ethanol solution, and acetic acid is added to adjust the pH value of the solution to 4.5-5.5; the hollow glass beads are placed in a mixer to be stirred at a low speed of 40-60 r/min, and a prepared silane coupling agent alcohol solution with the mass of 1-2.5% of the glass beads is added in a spraying mode to be treated for 5-15 min.
Example 1
Adding 61 parts of polypropylene, 14 parts of toughening agent, 5 parts of compatilizer, 0.2 part of antioxidant 1010 and 0.2 part of coupling agent into a high-speed mixer together, and mixing for 5 min.
And extruding and granulating the mixed blend through a double-screw extruder, simultaneously adding 12 parts of hollow glass microspheres and 8 parts of chopped glass fibers into the extruder from a side feed, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, the length-diameter ratio of an extrusion screw is 40, the rotating speed of the extrusion screw is 350 r/min from a feed section to a machine head, and the low-density, high-rigidity and high-toughness polypropylene composite material is obtained through melt blending and extrusion granulation.
Example 2
Adding 57 parts of polypropylene, 15 parts of toughening agent, 5 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.2 part of coupling agent and 0.1 part of dispersing agent into a high-speed mixer to mix for 10 min.
And extruding and granulating the mixed blend through a double-screw extruder, simultaneously adding 14 parts of hollow glass microspheres and 9 parts of chopped glass fibers into the extruder from a side feed, wherein the temperatures of all regions of the extruder are 170 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, the length-diameter ratio of an extrusion screw is 36, the rotating speed of the extrusion screw is 350 r/min from a feed section to a machine head, and the low-density, high-rigidity and high-toughness polypropylene composite material is obtained through melt blending and extrusion granulation.
Example 3
Adding 53 parts of polypropylene, 15 parts of toughening agent, 6 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.2 part of antioxidant DSTDP, 0.2 part of coupling agent and 0.1 part of lubricant into a high-speed mixer and mixing for 15 min.
Extruding and granulating the mixed blend through a double-screw extruder, simultaneously adding 16 parts of hollow glass microspheres and 10 parts of chopped glass fibers into the extruder from a side feed, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 195 ℃ in sequence from a feed section to a machine head, the length-diameter ratio of an extrusion screw is 40, the rotating speed of the extrusion screw is 350 r/min, and the low-density, high-rigidity and high-toughness polypropylene composite material is obtained through melt blending, extrusion and granulation.
Example 4
Adding 51 parts of polypropylene, 16 parts of toughening agent, 5 parts of compatilizer, 0.1 part of antioxidant 168, 0.1 part of antioxidant 1010, 0.1 part of antioxidant DSTDP, 0.2 part of coupling agent, 0.1 part of lubricant and 0.1 part of dispersant into a high-speed mixer to mix for 5 min.
Extruding and granulating the mixed blend through a double-screw extruder, simultaneously adding 18 parts of hollow glass microspheres and 10 parts of chopped glass fibers into the extruder from a side feed, wherein the temperature of each zone of the extruder is 160 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 195 ℃ in sequence from a feed section to a machine head, the length-diameter ratio of an extrusion screw is 44, the rotating speed of the extrusion screw is 300 revolutions per minute, the length-diameter ratio of the extrusion screw is 40, the rotating speed of the extrusion screw is 350 revolutions per minute, and the low-density, high-rigidity and high-toughness polypropylene composite material is obtained through melt blending, extrusion and granulation
Example 5
Adding 45 parts of polypropylene, 17 parts of toughening agent, 7 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.1 part of coupling agent, 0.1 part of lubricant and 0.1 part of dispersant into a high-speed mixer to mix for 10 min.
And extruding and granulating the mixed blend through a double-screw extruder, simultaneously adding 20 parts of hollow glass microspheres and 11 parts of chopped glass fibers into the extruder from a side feed, wherein the temperatures of all regions of the extruder are 160 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, the length-diameter ratio of an extrusion screw is 36, the rotating speed of the extrusion screw is 400 r/min, and the low-density, high-rigidity and high-toughness polypropylene composite material is obtained through melt blending and extrusion granulation.
Example 6
42 parts of polypropylene, 18 parts of toughening agent, 8 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.2 part of coupling agent, 0.2 part of lubricant and 0.1 part of dispersant are added into a high-speed mixer together and mixed for 15 min.
And extruding and granulating the mixed blend through a double-screw extruder, simultaneously adding 20 parts of hollow glass microspheres and 12 parts of chopped glass fibers into the extruder from a side feed, wherein the temperatures of all regions of the extruder are 160 ℃, 170 ℃, 175 ℃, 185 ℃, 190 ℃, the length-diameter ratio of an extrusion screw is 40, the rotating speed of the extrusion screw is 400 r/min, and the low-density, high-rigidity and high-toughness polypropylene composite material is obtained through melt blending and extrusion granulation.
The low density, high stiffness, high toughness polypropylene composites prepared in examples 1-6 were tested for performance and the results are shown in table 1.
TABLE 1
Comparative example 1
Mixing 61 parts of polypropylene copolymer, 14 parts of toughening agent, 12 parts of talcum powder, 5 parts of compatilizer, 0.2 part of antioxidant and 0.2 part of coupling agent in a high-speed mixer for 5min, extruding and granulating the mixed blend through a double-screw extruder, adding 8 parts of chopped glass fiber through side feeding, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ from a feeding section to a machine head in sequence, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 revolutions per minute.
Comparative example 2
61 parts of polypropylene copolymer, 8 parts of talcum powder, 14 parts of toughening agent, 12 parts of hollow glass beads, 5 parts of compatilizer, 0.2 part of antioxidant and 0.2 part of coupling agent are mixed in a high-speed mixer for 5min, the mixed blend is extruded and granulated by a double-screw extruder, the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, the length-diameter ratio of an extrusion screw is 40 and the rotating speed of the extrusion screw is 350 revolutions per minute from the feeding section to the head section.
Comparative example 3
Mixing 61 parts of polypropylene copolymer, 8 parts of chopped glass fiber, 14 parts of toughening agent, 12 parts of hollow glass beads, 5 parts of compatilizer, 0.2 part of antioxidant and 0.2 part of coupling agent in a high-speed mixer for 5min, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 revolutions per minute.
The materials prepared in comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in Table 2.
TABLE 2
| Test item/Unit | Test standard | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Finger melt/g/10 min | ISO 1133 | 19.8 | 24.2 | 25.6 | 20.5 |
| Tensile strength/MPa | ISO 527 | 20.4 | 19.8 | 18.8 | 19.5 |
| Flexural strength/MPa | ISO 178 | 31.6 | 30.2 | 25.8 | 30.5 |
| Flexural modulus/MPa | ISO 178 | 2082 | 1750 | 1255 | 1655 |
| Izod notched impact Strength/KJ/m2 | ISO 180 | 20.4 | N | 22.1 | 10.5 |
| Density/g/cm3 | ISO 1183 | 0.921 | 1.056 | 0.924 | 1.012 |
As can be seen from the data in tables 1 and 2, the composite material prepared by the method has higher strength and toughness, has the density reduced by 14.7 percent compared with the conventional PP + EPDM-T20 material, and meets the requirement of the lightweight material on the weight performance.
The low-density, high-rigidity and high-toughness polypropylene composite material adopts the high-crystallinity copolymerized polypropylene as a base material, and provides a basic guarantee for obtaining high rigidity of the prepared composite material; meanwhile, the hollow glass beads with the compressive strength of more than or equal to 20MPa are selected, and the crushing rate of the hollow glass beads is reduced in a side feeding processing mode, so that the density of the composite material is reduced fundamentally; the silane coupling agent is used for treating the surfaces of the glass beads, and the compatilizer with high maleic anhydride content is added, so that the bonding strength of the glass beads, the glass fibers and the polypropylene is enhanced, and the finally prepared composite material has higher strength;the invention discloses a polypropylene composite material which has the tensile strength of more than 20MPa, the flexural modulus of more than 2000MPa and the notch impact strength of more than 20KJ/m2Has good sensitivity and toughness, and the density is only 0.88-0.92g/cm3And the requirement of light weight is met.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A low-density, high-rigidity and high-toughness polypropylene composite material is characterized in that: the composition is prepared from the following components in parts by weight:
42-61 parts of polypropylene, namely polypropylene,
8-12 parts of chopped glass fiber,
14-18 parts of a toughening agent,
12-20 parts of hollow glass micro-beads,
5-8 parts of a compatilizer,
0.2 to 0.5 portion of antioxidant,
0.2 to 0.5 portion of other auxiliary agents.
2. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the polypropylene is high-crystalline co-polypropylene.
3. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the chopped glass fiber is alkali-free glass fiber, the diameter D is 5.0-15.0 μm, and the length is 4 mm.
4. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the toughening agent is at least one of ethylene-octene copolymer and ethylene-propylene copolymer, the melt flow rate of the toughening agent is 0.5-20 g/10min under the condition of 190 ℃/2.16kg, and the density of the toughening agent is 0.86-0.89g/cm3。
5. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the particle size D50 of the hollow glass bead is 5-30 mu m, and the density is 0.4-0.6g/cm3The compressive strength is more than or equal to 20MPa, and the hollow glass microspheres are surface-treated by a silane coupling agent.
6. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 5 wherein: the processing method comprises preparing 25% (mass ratio) ethanol solution with silane coupling agent, and adding acetic acid to adjust pH to 4.5-5.5; the hollow glass beads are placed in a mixer to be stirred at a low speed of 40-60 r/min, and a prepared silane coupling agent alcohol solution with the mass of 1-2.5% of the glass beads is added in a spraying mode to be treated for 5-15 min.
7. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the compatilizer is one or a mixture of more of maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted polypropylene and maleic anhydride grafted polypropylene, wherein the content of maleic anhydride is 1.5-3.5%.
8. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl thiodipropionate.
9. A low density, high stiffness, high toughness polypropylene composite as claimed in claim 1 wherein: the other auxiliary agents comprise a coupling agent, a lubricating agent and a dispersing agent.
10. A process for the preparation of a low density, high stiffness, high toughness polypropylene composite as claimed in any one of claims 1 to 9 wherein: the method comprises the following steps:
(1) 42-61 parts of polypropylene, 14-18 parts of toughening agent, 5-8 parts of compatilizer, 0.2-0.5 part of antioxidant and 0.2-0.5 part of other auxiliary agent are mixed and added into a high-speed mixer to be mixed for 5-15 min;
(2) adding the uniformly mixed materials obtained in the step (1) into a double-screw extruder, adding 8-12 parts of chopped glass fiber and 12-20 parts of hollow glass beads into a side feeding port of the double-screw extruder, and melting, blending and extruding the materials together to obtain a low-density, high-rigidity and high-toughness polypropylene composite material;
wherein, the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
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